CN105273173B - High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure and preparation method thereof - Google Patents
High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure and preparation method thereof Download PDFInfo
- Publication number
- CN105273173B CN105273173B CN201510817559.8A CN201510817559A CN105273173B CN 105273173 B CN105273173 B CN 105273173B CN 201510817559 A CN201510817559 A CN 201510817559A CN 105273173 B CN105273173 B CN 105273173B
- Authority
- CN
- China
- Prior art keywords
- copolyesters
- construction unit
- retardant
- unit number
- base structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure disclosed by the invention is on the basis of I, II polyester structural units represented, introduce and be made up of through random copolymerization III or IV construction unit represented, the intrinsic viscosity [η] of gained copolyesters is 0.30～1.10dL/g, and limited oxygen index is 24.0～40.0%；Vertical combustion grade V 2～V 0 grades；In taper calorimetric test, peak heat rate of release p HRR reduces by 33～83% than pure PET.The invention also discloses its preparation method.The crosslinked group that present invention introduces is Schiff's base group, flame-retardant and anti-dripping efficiency is high, thus without adding other fire retardants, just can improve rapidly the melt viscosity of polyester by become charcoal effect and stable " chemical crosslinking " of self-cross linking groups, thus give fire-retardant, the anti-dropping performance that copolyesters is excellent.
Description
Technical field
The invention belongs to high-temperature self-crosslinking flame-retardant anti-dripping copolyester and preparing technical field thereof.Specifically, the present invention relates to one
Class contains schiff base structure copolyesters with high temperature self-crosslinkable, fire-retardant and anti-dropping and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) with its high-modulus, high intensity, high resiliency, outstanding shape-retaining ability, thermostability
And chemical resistance, good case hardness and glossiness, in synthetic fibers, not only account for great share, simultaneously as engineering
Plastics have also played great effect in the life of people.But, the shortcoming of the inflammable and easy melted drippage that polyester self is intrinsic,
It is made to be restricted in the application of some key areas, such as electronic device, fire retardant protective clothing and military uniform, the vehicles and high-rise guest
Shop fabric etc..
Phosphorus flame retardant is that (Wang Yuzhong writes fire retardant maximally effective to copolyesters, the flame-retarded design of copolyester fiber, Sichuan science and technology
Publishing house, 1994), but this based flame retardant is by promoting that molten drop takes away the purpose that heat reaches fire-retardant.Due to copolyesters
The temperature of melt is the highest, not only contacts and can cause burn, and the molten drop dripped often causes second-time burning, so
Use traditional phosphonium flame retardant that polyester carries out the fire-retardant problem the most inevitably producing melted drippage.
In order to solve this problem, the molten or anti-dropping agent of infusibility by blended interpolation, such as politef and derivant etc. thereof,
Or interpolation inorganic filler, such as glass, silicon dioxide etc., can give the character (ZL of polyester anti-dropping
201010124613.8).It is used in conjunction with this kind of material and conventional flame retardant, polyester can be made to obtain certain flame-retardant and anti-dripping effect
Really, but their addition is big, makes gained polyester can not can only be used as engineering plastics for carrying out spinning and processing film forming, because of
This limits its range of application.
Summary of the invention
The problem that it is an object of the invention to exist for prior art, it is provided that what a class was new has the high-temperature self-crosslinking of schiff base structure
Flame-retardant anti-dripping copolyester, this copolyesters not only cost of material is low, it is easy to industrialization, it is also possible to directly as engineering plastics, thin
Film materials and fibrous raw material use, and prepared product at high temperature can be chemically crosslinked, thus improve copolyesters
Melt viscosity, and then give the flame-retardant and anti-dripping performance of copolyesters product fine.
The two of the purpose of the present invention are to provide the preparation method of above-mentioned high-temperature self-crosslinking flame-retardant anti-dripping copolyester.
The high-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure that the present invention provides, this copolyesters be by following I,
The construction unit composition that II and III or I, II and IV represents:
In formula, R1Represent arlydene,
In formula, R2Represent C2～C8Alkylidene,
In formula, Z1For H atom, hydroxyl, methyl or methoxy.
In formula, R3Represent C2～C8Alkylidene, Z1For H atom, hydroxyl, methyl or methoxy, Z2For H atom, methyl,
Methoxyl group or phenyl.
Wherein, the 0.5～20% of the construction unit number that construction unit number is I of III, the construction unit number of II: the structure of [I+III]
Unit number=1；The 0.5～20% of the construction unit number that construction unit number is I of IV, I: construction unit number=1 of [II+IV], respectively
Construction unit or its segment formed are arbitrarily to connect combination, and the intrinsic viscosity [η] of this copolyesters by carboxyl and hydroxy functional group
Being 0.30～1.10dL/g, limited oxygen index is 24.0～40.0%；Vertical combustion grade V-2～V-0 level；Peak in taper calorimetric test
Value HRR p-HRR reduces by 33～83% than pure PET.
In above-mentioned copolyesters the 5～15% of the construction unit number that construction unit number is I of preferably III, the construction unit number of II: [I+
III] construction unit number=1；The 5～15% of the construction unit number that construction unit number is I of IV, I: the construction unit of [II+IV]
Counting=1, and the intrinsic viscosity [η] of this copolyesters is 0.60～0.84dL/g, limited oxygen index is 28.0～40.0%；Vertical combustion etc.
Level is V-1～V-0 level；In taper calorimetric test, peak heat rate of release p-HRR reduces by 42～83% than pure PET.
The preparation method of above-mentioned based on schiff base structure the high-temperature self-crosslinking flame-retardant anti-dripping copolyester that the present invention provides, the method
It is by binary acid or its carboxylate and C2～C8The copolyesters monomer of polyhydric alcohol, catalyst according to conventional proportioning, often use
After the direct esterification of rule or ester-interchange method are esterified, it is prepared from through polycondensation reaction, it is characterised in that in ester exchange reaction
Before or ester exchange reaction aftercondensated before, add in reaction system by moles the hundred of binary acid in copolyesters monomer or its carboxylate
Mark is calculated as the self-crosslinking flame-retardant monomer containing schiff base structure unit of 0.5～20%, preferably 5～15%.
The self-crosslinking flame-retardant monomer containing schiff base structure unit used by above method is any one in following general structure:
In formula, X1For carboxyl or ester group, Y1For C2-C8Primary alcohol group, Z1For H atom, hydroxyl, methyl or methoxy,
Z2For H atom, methyl, methoxyl group or phenyl.
Any one in the preferred following general structure of the self-crosslinking flame-retardant monomer containing schiff base structure unit used by above method:
In formula, X1For carboxyl or ester group, Y1For C2～C8Primary alcohol group, Z1For methyl or methoxy, Z2For methyl, methoxy
Base or phenyl, and when during the amount of being simultaneously introduced is by copolyesters monomer, the mole percent of binary acid or its carboxylate is calculated as 5～15%,
The intrinsic viscosity [η] of this copolyesters is 0.62～0.81dL/g, and limited oxygen index is 31.0～40.0%；Vertical combustion grade is V-0
Level；In taper calorimetric test, peak heat rate of release p-HRR reduces by 71～83% than pure PET.
Conventional direct esterification of the present invention or the processing step of ester-interchange method and condition are specific as follows:
Direct esterification: adding polyester monocase, catalyst and schiff base structure monomer by proportioning in a kettle., pressurization is warmed up to
200～210 DEG C carry out esterification 2～6 hours；After esterification terminates, little in 220～250 DEG C of polycondensation reactions 0.5～1.5 under coarse vacuum
Time, the most under a high vacuum in 230～260 DEG C of polycondensations 1～3 hours, extrude melt, water-cooled with nitrogen, obtain target copolyesters.
Wherein, reactor is added before schiff base structure monomer may select the polycondensation before esterification or after esterification.
Ester-interchange method: adding polyester monocase, catalyst and schiff base structure monomer by proportioning in a kettle., normal pressure is in 180～210
DEG C carry out ester exchange reaction 3～5 hours；After ester exchange terminates, in 220～250 DEG C of polycondensations 0.5～1.5 hours under coarse vacuum, then
Under a high vacuum in 230～260 DEG C of polycondensations 1～3 hours, extrude melt, water-cooled with nitrogen, obtain target copolyesters.Wherein,
Schiff base structure monomer adds reactor before may select the polycondensation before ester exchange or after ester exchange.
Catalyst selected in above method is zinc acetate, manganese acetate, cobaltous acetate, antimony oxide, antimony glycol and metatitanic acid
At least one in four butyl esters.
The invention have the advantages that
1, containing aromatic schiff base structure in the construction unit of the high-temperature self-crosslinking flame-retardant anti-dripping copolyester provided due to the present invention,
Big conjugated structure can be formed between its carbon-to-nitrogen double bon and phenyl ring, thus under the synthesis and processing temperature (220～260 DEG C) of copolyesters
It is stable, will not decompose and self-crosslinking, thus not interfere with synthesis and the processing of polyester.But when it reaches at heated combustion
Front to heat decomposition temperature (380～400 DEG C), quick chemical heat can be occurred to cross-link by molecular rearrangement cyclization, improves rapidly
Copolyesters melt viscosity at high temperature, promotes to become under its high temperature charcoal, forms barrier layer, thus obtains the fire-retardant and anti-molten of excellence
Drip effect.
2, the copolyesters provided due to the present invention is because copolyesters molecular chain movement is limited in the generating process of chemical crosslinking, has few
Part schiff base structure group is not engaged in crosslinking, the uncrosslinked nitrogen-containing group of this part can when burning release nitrogen, thus one
Aspect can play expanded foamed effect, promotes that copolyesters at high temperature forms foamed char (seeing accompanying drawing 3) and plays very well
Heat insulation oxygen barrier effect promoting fire resistance and anti-dropping effect, on the other hand in burning, the release of nitrogen can also dilute combustion
The oxygen concentration of environment so that copolyesters shows better flame resistance in burning.
3, the cross-linking efficiency of the high-temperature self-crosslinking flame-retardant anti-dripping copolyester provided due to the present invention is high, only need to introduce minor proportion (≤
Self-crosslinking flame-retardant monomer 15mol%), copolyesters i.e. can reach the most fire-retardant and anti-dropping effect, thus can reduce preparation
Cost.
4, the high-temperature self-crosslinking flame-retardant anti-dripping copolyester non-halogen non-phosphate provided due to the present invention, thus belong to environment-friendly material.
5, owing to the copolyesters of present invention offer being not added with affecting additive prepared by fiber, thus not only can be directly as fiber
Fire-retardant, anti-dropping copolyesters, it is also possible to as the macromole bulking agent of immiscible polymer blends, be allowed to improve
The fire-retardant of material and the purpose of anti-dropping modification also can be given while material mechanical performance.
6, due to the present invention provide preparation method with the method being conventionally synthesized copolyesters substantially coincident, thus have maturation
Technique, operate simply and easily so that this copolyesters is highly susceptible to industrialized production.
Accompanying drawing explanation
Fig. 1 is the high-temperature self-crosslinking flame-retardant anti-dripping copolyester BA of the embodiment of the present invention 10 preparation15The infrared spectrum spectrogram of PET.
It can be seen that at 1630cm-1Place occurs in that the characteristic absorption peak of carbon-to-nitrogen double bon, illustrates that schiff base structure is by successfully
It is incorporated in copolyesters chain.
Fig. 2 is that pure PET prepared by comparative example of the present invention is common with the high-temperature self-crosslinking flame-retardant and anti-dripping of the embodiment of the present invention 10 preparation
Polyester BA15Simultaneous thermal analysis test (TG-DSC) spectrogram of PET.It will be seen that pure PET is molten from DSC curve
Directly occur in that decomposition endothermic peak after melting peak, and high-temperature self-crosslinking flame-retardant anti-dripping copolyester goes out between melting peak and decomposition peak
Show crosslinking exothermic peak, shown that this copolyesters at high temperature may occur from cross-linking reaction, and do not affect processing and preparation.
Fig. 3 is that pure PET prepared by comparative example of the present invention is common with the high-temperature self-crosslinking flame-retardant and anti-dripping of the embodiment of the present invention 10 preparation
Polyester BA15(complex viscosity is the immediate cause affecting copolyesters flame-retardant and anti-dripping to the dynamic rheological property figure of PET, in general, multiple
Number viscosity is the biggest, and melt viscosity is the highest, and anti-dropping effect is the best).It can be seen that pure PET is with the rising of temperature,
Complex viscosity drastically declines, the trend that the complex viscosity of copolyesters raises rapidly after then presenting first reduction, further illustrates this altogether
Polyester can at high temperature occur self-crosslinking reaction.
Fig. 4 is that pure PET prepared by comparative example of the present invention is common with the high-temperature self-crosslinking flame-retardant and anti-dripping of the embodiment of the present invention 10 preparation
Polyester BA15One-tenth charcoal effect photo after the test of PET limited oxygen index, it can be seen that the copolyesters that the present invention is obtained
Fire-retardant one-tenth charcoal effect is obvious, has extraordinary anti-dropping performance.
Detailed description of the invention
Embodiment is given below so that the invention will be further described.Be necessary it is pointed out here that be following example it is not intended that
Limiting the scope of the invention, if the present invention is made one according to the invention described above content by the person skilled in the art in this field
A little nonessential improvement and adjustment, still fall within scope.
It addition, what deserves to be explained is: 1) high-temperature self-crosslinking based on aromatic schiff base structure of following example gained is fire-retardant anti-molten
The intrinsic viscosity [η] dripping copolyesters is all for solvent with phenol/sym.-tetrachloroethane (1:1, v:v), and being configured to concentration is 0.5g/dL
Solution, with dark type viscometer 25 DEG C test；2) limited oxygen index of test product be all be made into 120 × 6.5 ×
3.2mm3Standard oxygen exponential spline, according to ASTM D2863-97 standard, HC-2 oxygen index instrument measures；3) hang down
It is then to be made into 120 × 12.7 × 3.2mm that direct combustion burns3Standard batten, according to UL-94 standard, use CZF-2 type vertical
(UL-94) that combustion instrument measures；4) taper calorimetric test is made into 100 × 100 × 3mm3Standard batten, according to ISO
5660-1 standard, on FTT cone calorimetry, with irradiation power as 50kW/m2It is measured.
Embodiment 1
By 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 18.1g 4-(2-hydroxyl-oxethyl) benzaldehyde contracting 4-(2-hydroxyl
Base oxethyl) aniline Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, and inflated with nitrogen gets rid of kettle
Interior air, normal pressure carries out ester exchange reaction 3～5 hours in 180～210 DEG C；After ester exchange terminates, in 220～250 under coarse vacuum
DEG C polycondensation 0.5～1.5 hours, (pressure ＜ 60Pa) is after 230～260 DEG C of polycondensations 1～3 hours the most under a high vacuum, discharging,
Water-cooled.
The intrinsic viscosity [η] of this copolyesters is 0.71dL/g；Limited oxygen index is 25.5%；Vertical combustion grade is V-2, taper
In calorimetric test, peak heat rate of release p-HRR is 704kW/m2。
Embodiment 2
By 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 30.1g 4-(2-hydroxyl-oxethyl) benzaldehyde contracting 4-(2-hydroxyl
Base oxethyl) aniline Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, be given by embodiment 1
Step and after condition carries out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.66dL/g；Limited oxygen index is 28.0%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 624kW/m2。
Embodiment 3
By 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 60.2g 4-(2-hydroxyl-oxethyl) benzaldehyde contracting 4-(2-hydroxyl
Base oxethyl) aniline Schiff's base, 2.2g zinc acetate and 0.16g antimony oxide join in reactor, be given by embodiment 1
Step and after condition carries out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.67dL/g；Limited oxygen index is 29.5%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 546kW/m2。
Embodiment 4
By 388g dimethyl terephthalate (DMT), 240mL1,3-propylene glycol, 131.6g 4-(3-hydroxy propyloxy group) benzaldehyde contracting 4-(3-
Hydroxy propyloxy group) aniline Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, give by embodiment 1
After the step gone out and condition carry out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.44dL/g；Limited oxygen index is 26.0%；Vertical combustion grade is V-2, taper
In calorimetric test, peak heat rate of release p-HRR is 675kW/m2。
Embodiment 5
388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 121.2g 4-(2-hydroxyl-oxethyl) benzaldehyde are contracted to benzene
Diamidogen Bis-Schiff Bases, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and
After condition carries out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.60dL/g；Limited oxygen index is 30.5%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 521kW/m2。
Embodiment 6
By 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 5.9g benzaldehyde contracting 5-amino isophthalic acid dimethyl ester seat
Husband's alkali, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, and the step be given by embodiment 1 and condition are carried out
After ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.90dL/g；Limited oxygen index is 24.5%；Vertical combustion grade is V-2, taper
In calorimetric test, peak heat rate of release p-HRR is 693kW/m2。
Embodiment 7
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 17.8g benzaldehyde contracting 5-amino isophthalic acid diformazan
Ester Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and condition
After carrying out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.85dL/g；Limited oxygen index is 26.0%；Vertical combustion grade is V-2, taper
In calorimetric test, peak heat rate of release p-HRR is 623kW/m2。
Embodiment 8
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 29.7g benzaldehyde contracting 5-amino isophthalic acid diformazan
Ester Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and condition
After carrying out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.82dL/g；Limited oxygen index is 28.0%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 502kW/m2。
Embodiment 9
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 41.6g benzaldehyde contracting 5-amino isophthalic acid diformazan
Ester Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and condition
After carrying out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.80dL/g；Limited oxygen index is 30.0%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 481kW/m2。
Embodiment 10
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 59.4g benzaldehyde contracting 5-amino isophthalic acid diformazan
Ester Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and condition
After carrying out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.79dL/g；Limited oxygen index is 34.0%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 425kW/m2。
Embodiment 11
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 89.1g benzaldehyde contracting 5-amino isophthalic acid diformazan
Ester Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and condition
After carrying out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.84dL/g；Limited oxygen index is 36.0%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 389kW/m2。
Embodiment 12
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 118.8g benzaldehyde contracting 5-amino isophthalic acid diformazan
Ester Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and condition
After carrying out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.77dL/g；Limited oxygen index is 31.0%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 374kW/m2。
Embodiment 13
First by 388g dimethyl terephthalate (DMT), 275mL1,4-butanediol, 116.1g 2-methoxyl group-4-(4-hydroxybutoxy)
Benzaldehyde contracting 4-(4-hydroxybutoxy) aniline Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor,
After the step be given by embodiment 1 and condition carry out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.63dL/g；Limited oxygen index is 31.0%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 327kW/m2。
Embodiment 14
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 113.1g 2-phenyl-4-(2-hydroxyl-oxethyl) benzene first
Al 4-(2-hydroxyl-oxethyl) aniline Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, press
After step that embodiment 1 is given and condition carry out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.64dL/g；Limited oxygen index is 32.5%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 290kW/m2。
Embodiment 15
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 18.8g hydroxy benzaldehyde contracting 5-amino isophthalic diformazan
Dimethyl phthalate Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1
After carrying out ester exchange and polycondensation reaction with condition, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.87dL/g；Limited oxygen index is 28.0%；Vertical combustion grade is V-2, taper
In calorimetric test, peak heat rate of release p-HRR is 618kW/m2。
Embodiment 16
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 93.9g hydroxy benzaldehyde contracting 5-amino isophthalic diformazan
Dimethyl phthalate Schiff's base, 2.2g zinc acetate and 0.16g antimony glycol join in reactor, the step be given by embodiment 1 and
After condition carries out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.69dL/g；Limited oxygen index is 33.5%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 275kW/m2。
Embodiment 17
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 62.2g 2-tolyl aldehyde contracting 5-amino terephthaldehyde
Dimethyl phthalate Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1
After carrying out ester exchange and polycondensation reaction with condition, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.75dL/g；Limited oxygen index is 33.0%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 263kW/m2。
Embodiment 18
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 93.3g 2-tolyl aldehyde contracting 5-amino terephthaldehyde
Dimethyl phthalate Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1
After carrying out ester exchange and polycondensation reaction with condition, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.70dL/g；Limited oxygen index is 38.5%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 226kW/m2。
Embodiment 19
First by 332g p-phthalic acid, 210mL ethylene glycol, 31.4g m-methoxybenzaldehyde contracting 5-amino isophthalic acid seat
Husband's alkali, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, and pressurization is warmed up to 200～210 DEG C and carries out esterification instead
Answer 2～6 hours；After esterification terminates, in 220～250 DEG C of polycondensation reactions 0.5～1.5 hours under coarse vacuum, (＜ the most under a high vacuum
60Pa) after 230～260 DEG C of polycondensations 1～3 hours, discharging, water-cooled.
The intrinsic viscosity [η] of this copolyesters is 0.81dL/g；Limited oxygen index is 31.0%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 314kW/m2。
Embodiment 20
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 86.4g 2-tolyl aldehyde contracting 5-amino terephthaldehyde
Dimethyl phthalate Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1
After carrying out ester exchange and polycondensation reaction with condition, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.62dL/g；Limited oxygen index is 40.0%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 187kW/m2。
Embodiment 21
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 1.35g p-carboxybenzaldehyde contracting para-amino benzoic acid seat
Husband's alkali, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, and the step be given by embodiment 1 and condition are carried out
After ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 1.10dL/g；Limited oxygen index is 24.0%；Vertical combustion grade is V-2, taper
In calorimetric test, peak heat rate of release p-HRR is 726kW/m2。
Embodiment 22
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 49.35g benzaldehyde contracting 2,5-bis-(3-hydroxy propyloxy group)
Aniline Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and bar
After part carries out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.71dL/g；Limited oxygen index is 36.5%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 467kW/m2。
Embodiment 23
First 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 85.6g 3-methyl 4-aldehyde benzoic acid methyl ester are contracted to benzene
Diamidogen Bis-Schiff Bases, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1 and
After condition carries out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.30dL/g；Limited oxygen index is 24.5%；Vertical combustion grade is V-2, taper
In calorimetric test, peak heat rate of release p-HRR is 687kW/m2。
Embodiment 24
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 31.7g salicylaldhyde contracting 3,5-bis-(2-hydroxyl second
Epoxide) aniline Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1
After rapid and condition carries out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.78dL/g；Limited oxygen index is 37.5%；Vertical combustion grade is V-0, taper
In calorimetric test, peak heat rate of release p-HRR is 235kW/m2。
Embodiment 25
First by 388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 63.4g salicylaldhyde contracting 3,5-bis-(2-hydroxyl second
Epoxide) aniline Schiff's base, 2.2g zinc acetate and 0.16g butyl titanate join in reactor, the step be given by embodiment 1
After rapid and condition carries out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.80dL/g；Limited oxygen index is 35.0%；Vertical combustion grade is V-1, taper
In calorimetric test, peak heat rate of release p-HRR is 412kW/m2。
Comparative example
388g dimethyl terephthalate (DMT), 210mL ethylene glycol, 2.2g zinc acetate and 0.16g butyl titanate are joined instead
Answer in still, after the step be given by embodiment 1 and condition carry out ester exchange and polycondensation reaction, discharging.
The intrinsic viscosity [η] of this copolyesters is 0.72dL/g；Limited oxygen index is 21.0%；Vertical combustion grade is stepless (N.R.),
In vertical combustion, molten drop is the most serious；In taper amount heat amount test, peak heat rate of release p-HRR is 1087kW/m2。
Claims (5)
1. high-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure, this copolyesters be by following I, II and III or I,
The construction unit composition that II and IV represents:
In formula, R1Represent arlydene,
In formula, R2Represent C2～C8Alkylidene,
In formula, Z1For H atom, hydroxyl, methyl or methoxy,
In formula, R3Represent C2～C8Alkylidene, Z1For H atom, hydroxyl, methyl or methoxy, Z2For H atom, methyl,
Methoxyl group or phenyl,
Wherein, the 0.5～20% of the construction unit number that construction unit number is I of III, the construction unit number of II: the structure of [I+III]
Unit number=1；The 0.5～20% of the construction unit number that construction unit number is I of IV, I: construction unit number=1 of [II+IV], respectively
Construction unit or its segment formed are arbitrarily to connect combination, and the intrinsic viscosity [η] of this copolyesters by carboxyl and hydroxy functional group
Being 0.30～1.10dL/g, limited oxygen index is 24.0～40.0%；Vertical combustion grade V-2～V-0 level；Peak in taper calorimetric test
Value HRR p-HRR reduces by 33～83% than pure PET.
High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure the most according to claim 1, in this copolyesters
The 5～15% of the construction unit number that construction unit number is I of III, the construction unit number of II: construction unit number=1 of [I+III]；Ⅳ
The construction unit number that construction unit number is I 5～15%, I: construction unit number=1 of [II+IV], and the characteristic of this copolyesters
Viscosity number [η] is 0.60～0.84dL/g, and limited oxygen index is 28.0～40.0%；Vertical combustion grade is V-1～V-0 level；Taper amount
In Thermal test, peak heat rate of release p-HRR reduces by 42～83% than pure PET.
The preparation method of high-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure the most according to claim 1,
The method is by aromatic diacid or its carboxylate and C2～C8The copolyesters monomer of dihydroxylic alcohols, catalyst joins according to conventional
Ratio, after using conventional direct esterification or ester-interchange method to be esterified, is prepared from through polycondensation reaction, it is characterised in that
Before direct esterification reaction or before direct esterification reaction aftercondensated, or before ester exchange reaction or before ester exchange reaction aftercondensated, in reaction
System adds by the mole percent of aromatic diacid or its carboxylate in copolyesters monomer be calculated as 0.5～20% containing Schiff's base
The self-crosslinking flame-retardant monomer of construction unit,
The self-crosslinking flame-retardant monomer containing schiff base structure unit used by the method is any one in following general structure:
In formula, X1For carboxyl or ester group, Y1For C2～C8Primary alcohol group, Z1For H atom, hydroxyl, methyl or first
Epoxide, Z2For H atom, methyl, methoxyl group or phenyl.
The preparation method of high-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure the most according to claim 3,
The method adds in reaction system and is calculated as 5～15% by the mole percent of aromatic diacid or its carboxylate in copolyesters monomer
The self-crosslinking flame-retardant monomer containing schiff base structure unit.
5. according to the preparation side of the high-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure described in claim 3 or 4
Method, the self-crosslinking flame-retardant monomer containing schiff base structure unit used by the method is any one in following general structure:
In formula, X1For carboxyl or ester group, Y1For C2～C8Primary alcohol group, Z1For methyl or methoxy, Z2For methyl, methoxy
Base or phenyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510817559.8A CN105273173B (en) | 2015-11-20 | 2015-11-20 | High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510817559.8A CN105273173B (en) | 2015-11-20 | 2015-11-20 | High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105273173A CN105273173A (en) | 2016-01-27 |
| CN105273173B true CN105273173B (en) | 2016-11-30 |
Family
ID=55143058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510817559.8A Active CN105273173B (en) | 2015-11-20 | 2015-11-20 | High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105273173B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107353602B (en) * | 2016-05-09 | 2019-07-05 | 上海越科复合材料有限公司 | A method of preparing the sandwich PET foamed material of wind power generation blade |
| CN107022085B (en) * | 2017-03-09 | 2020-02-28 | 四川大学 | High-temperature crosslinking flame retardant with Schiff base and phosphorus/phosphonyl structure as well as preparation method and application thereof |
| CN109517152B (en) * | 2017-09-20 | 2020-08-11 | 四川大学 | High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzamide structure and preparation method and application thereof |
| CN108395526B (en) * | 2018-02-09 | 2020-03-10 | 四川大学 | Flame-retardant anti-dripping copolyester based on benzimidazole structure and preparation method thereof |
| CN110511368B (en) * | 2019-08-09 | 2021-07-27 | 浙江恒澜科技有限公司 | Vinyl nano-silicon sphere compounded high-temperature self-crosslinking flame-retardant anti-dripping copolyester and preparation method thereof |
| CN111187296B (en) * | 2019-08-26 | 2021-09-07 | 兰州理工大学 | Nickel ion flame-retardant complex with Schiff base structure |
| CN110511241B (en) * | 2019-08-26 | 2021-09-03 | 兰州理工大学 | N, N' -bis (2-hydroxy- (diphenyl phosphate) salicylidene) -1, 2-phenylenediamine nickel flame retardant and preparation method thereof |
| JP2023531467A (en) * | 2020-06-19 | 2023-07-24 | 四川大学 | Flame-retardant and anti-drip copolyester based on high temperature self-crosslinking and its preparation and application |
| CN114058001A (en) * | 2020-08-03 | 2022-02-18 | 中国科学院成都有机化学有限公司 | Flame-retardant anti-dripping copolyester and preparation method thereof |
| CN113461734A (en) * | 2021-04-19 | 2021-10-01 | 衡阳师范学院 | Novel Schiff base DOPO phosphorus nitrogen-containing flame retardant and synthesis method and application thereof |
| CN114478634A (en) * | 2022-01-20 | 2022-05-13 | 东华大学 | Aromatic Schiff base phosphazene double-base structure flame retardant and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3944525A (en) * | 1973-10-03 | 1976-03-16 | Ciba-Geigy Corporation | Crosslinked resins prepared from an N,N'-bis-imide and a schiff base |
| CN102732041A (en) * | 2012-05-29 | 2012-10-17 | 浙江大学宁波理工学院 | Phosphorus-containing Schiff base derivative intumescent fire retardant and preparation method thereof |
| CN102863611A (en) * | 2012-10-10 | 2013-01-09 | 四川大学 | Azobenzene structure based high-temperature self-cross-linked expanded flame-retardant anti-dripping copolyester and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01261406A (en) * | 1988-04-13 | 1989-10-18 | Mitsubishi Kasei Corp | Chlorinated polymeric compound |
-
2015
- 2015-11-20 CN CN201510817559.8A patent/CN105273173B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3944525A (en) * | 1973-10-03 | 1976-03-16 | Ciba-Geigy Corporation | Crosslinked resins prepared from an N,N'-bis-imide and a schiff base |
| CN102732041A (en) * | 2012-05-29 | 2012-10-17 | 浙江大学宁波理工学院 | Phosphorus-containing Schiff base derivative intumescent fire retardant and preparation method thereof |
| CN102863611A (en) * | 2012-10-10 | 2013-01-09 | 四川大学 | Azobenzene structure based high-temperature self-cross-linked expanded flame-retardant anti-dripping copolyester and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Thermal properties and flame retardancy of novel epoxy based on phosphorus-modified Schiff-base;Huan Liu et al;《Polymers for Advanced Technologies》;20101201;第23卷;114-121 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105273173A (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105273173B (en) | High-temperature self-crosslinking flame-retardant anti-dripping copolyester based on schiff base structure and preparation method thereof | |
| CN102863611B (en) | Azobenzene structure based high-temperature self-cross-linked expanded flame-retardant anti-dripping copolyester and preparation method thereof | |
| CN108395526B (en) | Flame-retardant anti-dripping copolyester based on benzimidazole structure and preparation method thereof | |
| TWI363817B (en) | Dope dyed flame retardant polyester fibers, textile products therefrom and the method of manufacturing thereof | |
| CN102174183B (en) | High-temperature self-crosslinking flame-retardant anti-dripping copolyester and preparation method thereof | |
| CN104592094B (en) | Monomer containing benzimide phenylacetylene structure, high temperature self-crosslinked copolyester and preparation method thereof | |
| CN110066389B (en) | Ionic monomer containing benzo-heterocycle sulfonate structure, flame-retardant anti-dripping ionomer using ionic monomer, and preparation methods and applications of ionic monomer and ionomer | |
| CN110016054B (en) | Ionic monomer containing phosphazene benzo heterocyclic structure, copolyester ionomer flame-retardant by using ionic monomer, and preparation method and application of ionic monomer and copolyester ionomer flame-retardant | |
| CN104710604B (en) | Branched crosslinking expansion melt-drip resistant inflaming retarding copolyesters based on triazine ring structure and preparation method thereof | |
| CN109517152B (en) | High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzamide structure and preparation method and application thereof | |
| CN108359084B (en) | High-temperature self-crosslinking flame-retardant smoke-suppression anti-dripping copolyester based on benzimide structure and preparation method thereof | |
| CN104119538A (en) | Flame retardant and preparation method thereof, and flame-retardant polyester and application thereof | |
| CN104231250A (en) | Cationic dyeable flame-retardant polyester and preparation method thereof | |
| CN101407577A (en) | Low-melting point phosphor-containing flame-retardant copolyester and preparation thereof | |
| CN113817152B (en) | Flame-retardant anti-dripping copolyester based on high-temperature self-crosslinking and preparation method and application thereof | |
| CA1045739A (en) | Fireproof polyester composition | |
| CN107189048B (en) | Low-smoke and flame retardant anti-dropping copolyesters based on fragrant nitrile structure and preparation method thereof | |
| CN102030894B (en) | Phosphoric terephthalic acid propylene glycol ester antiflaming block copolyester and preparation method thereof | |
| CN113817150B (en) | Copolyester containing aromatic secondary amine structure and preparation method and application thereof | |
| CN108383987A (en) | Height based on arone structure is at charcoal low-smoke and flame retardant anti-dropping copolyesters and preparation method thereof | |
| CN104478789A (en) | Copolyester crosslinking monomer, copolyester based on monomer and preparation method thereof | |
| Zamora et al. | Aromatic homo‐and copolyesters from naturally occurring monosaccharides: PET and PEI analogs derived from l‐arabinitol and xylitol | |
| JP2023531467A (en) | Flame-retardant and anti-drip copolyester based on high temperature self-crosslinking and its preparation and application | |
| JP7147440B2 (en) | Method for producing polyester composition | |
| Zamora et al. | Butylene copolyesters based on aldaric and terephthalic acids. Synthesis and characterization |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |